Quaternated 3,5-dimethylphenyl ethers



Patented Feb. 28,1950

QUATERNATED 3,5-DIMETHYLPHENYL ETHERS Peter L. de Benneville,Philadelphia, Pa., Leonard J. Armstrong, Wenona, Ill., and Louis H.Bock, Huntingdon Valley, Pa., assignors to Riihm & Haas Company,Philadelphia, Pa., a corporation of Delaware No Drawing. ApplicationAugust 19, 1947, Serial No. 769,528

5 Claims. 1

This invention deals with quaternary ammonium salts. More particularly,it concerns phenyl ethers in which phenyl rings carry two methyl groupsin the positions meta to the ether function and also carry quaternaryammonium roups bound thereto through a methylene linkage. The method ofpreparation of such compounds is also part of this invention.

Although it has already been proposed to react some halomethyl compoundswith amines to form quaternary ammonium compounds, the3,5-dimethylphenyl ethers having a quaternary ammonium methylsubstituents in the phenyl rings have not been known. These newcompounds have now been found to form a unique class having individualproperties-which set it apart from previously known quaternary compoundsor phenyl ethers.

The new compounds here described and claimed are characterized by thefacility with which they react with cellulose to yield new celluloseethers having a valuable new combination of properties. It has beenfound that the phenyl ethers of this invention, characterized by methylgroups in the 3- and 5-positions of the phenyl rings, the ether functionbeing accorded the one-position, and characterized by quaternaryammonium methyl groups, also as phenyl substituents, react withcellulose at the hydroxyl groups thereof, splitting out an amine saltand forming new cellulose ethers. This reaction occurs with relativeease under conditions of temperature and pressure which do not undulytender the treated cellulose. Somewhat similar quaternary compounds,lacking, however, the full configuration described, are not thusreactive nor effective in this way.

The compounds of this invention have the general formula v RI RI! l--:cm+ R0 I- x m m on cm wherein a is a number from zero to one; 11 is aninteger from one to two, m is an integer having a value from one up to avalue of 311; R is a member of the class consisting of alkyl groups andacyl groups of preferably one to eighteen carbon atoms; R0 is amonovalent aliphatic hydrocarbon group of one to eighteen carbon atomswhen n has a value of one and is a divalent aliphatic group from theclass consisting of alkylene groups of two to three carbon atoms andsaturated aliphatic ether chains having two to three carbon atomsbetween oxygen atoms when n has a value of two; R, taken individually,represents one of the groups from the class consisting of methyl, ethylallyl, methallyl, and benzyl groups; R" and R', taken individually,represent a methyl or ethyl group; R" and R', taken together, representa divalent saturated aliphatic group from the class consisting ofhydrocarbon chains and ether chains which jointly with the nitrogen forma heterocycle; R, R", and R', taken together, represent a trivalentunsaturated hydrocarbon chain which jointly with the nitrogen forms aheterocycle; and X is an anion, particularly a halogen.

The group R0, when monovalent, may be an aliphatic hydrocarbon group ofone to eighteen carbon atoms, preferably saturated. It may have astraight or branched chain and may be saturated or unsaturated- Typicalgroups for R0 as a monovalent hydrocarbon radical are methyl, ethyl,propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, cetyl, octadecyl, andisomers thereof including isopropyl, isobutyl, sec.-butyl, ethylhexyl,capryl, isononyl, 1-methyl-4-ethyloctyl, or 1-sec.- butyl-4-ethyloctyl,and unsaturated groups such as allyl, methallyl, crotyl, undecenyl, oroctadecenyl. Larger groups may be used, but are not readily available.The preparation of phenyl ethers is known and the usual methods may beapplied to the preparation of ethers of 3,5-dimethylphenol orsym.-xylenol.

When R0 is divalent, polyethers are formed. The phenyl groups form theterminal members thereof. Between the oxyphenyl groups there occurs anethylene or propylene chain or a divalent aliphatic ether chain in whichoxygen atoms are separated by alkylene chains of twov to three carbonatoms. Thus, R0 may be ethylene,

--CH2CHa-, trimethylene, CH2CH2CH2, propylene, CH (CH3) CH2---,ethoxyethyl, CH2CH2OCH2CH2, propoxypropyl,

CsHeOCsHaethoxyethoxyethyl,

CH2CH2OCH2CH2OCH2CH2 or the like, including CHzCH (CH3) 0 (CH3) CHCH2-The polyethers are formed from 3,5-dimethylphenol by reaction with adihaloethane or dihalopropane or with a dihaloalkyl ether, such asdichloroethyl ether, dibromotrimethylene, di-

bromopropyl ether, dichiorotriglycol, or the like, in the presence of astrong base.

The group R, when present, replaces one of the nuclear hydrogens. It maybe an alkyl group of one to eighteen carbon atoms, such as methyl,ethyl, propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, isooctyl,diisobutyl or tert.-octyl, decyl, dodecyl, cetyl, or octadecyl, or evenlarger groups such as tetracosyl. R may also represent an acyl group,such as acetyl, propionyl, butyryl, hexoyl, 2-ethylhexoyl, dodecanoyl,oleyl, or stearoyl, or larger group such as tetracosanoyl. Acyl groupsare readily introduced in the phenyl rings by the Friedel-Craftsreaction, as with aluminum chloride. They may be reduced, as with zincand acid, to the corresponding hydrocarbon group.

When R or R are groups containing five or more carbon atoms, theresulting compounds cause a profound change in the nature of celluloseupon reaction therewith. The new cellulose ethers formed thus withsubstituents of five or more carbon atoms are but slightly absorptive towater. With groups of twelve or more carbon atoms there is fairrepellency of water which is most marked when C16 to C24 groups arepresent. Since C16 and Cu; groups are the most readily available ofthese, these will usually be used for this purpose.

The reactive functional group of the compounds of this invention is thequaternary ammonium methyl substituent which replaces one or more of theavailable ring hydrogens. Where all three positions of the phenyl ring,the 2-, 4-, and 6-positions, are available for substitution, it ispossible to introduce one or two such substituents readily and in manycases a third in the same ring. When two rings are present, as in thepolyethers, each ring may be thus substituted. When an R group ispresent in the ring, it is, of course, possible to introduce only twoquaternary ammonium methyl groups.

As stated above, R, R", and R may be the specified individual groups. Aparticularly valuable subclass results, however, when R, R, or R' formparts of multivalent substituents. When all three are taken together, atrivalent unsaturated chain is at hand. It forms a heterocycle with thenitrogen, as in pyridine, alphapicoline, beta-picoline, quinoline,isoquinoline, or

other heterocyclic tertiary amine. When R and R' are taken together,they form a divalent saturated chain, which is either a hydrocarbonchain as in the CH2CH2CH2CH2 chain of pyrollidine, the CH2CH2CH2CH2CH2--chain of piperidine, or an aliphatic ether chain as in morpholine. Thesecyclic amines seem to have some fluxing effect when the quaternatedphenyl ethers are reacted with cellulose.

The introduction of the N-methyl substituent is accomplished through thesteps of halomethylating the phenyl ring or rings and convert'ng thehalomethylated compound to a quaternary ammonium salt. This may be doneby reacting the halomethylphenyl ether with a secondary amine, such asmorpholine, piperidine, pyrollidine, dimethylamine, diethylamine, or thelike, to form a tertiary amine which is then reacted with an alkylatingagent or aralkylating agent, such as methyl iodide, ethyl bromide, ethylsulfate, allyl chloride, or the like. Alternatively, thehalomethylphenyl ether is reacted with a tertiary amine, such astrimethylamine, ethyldimethylamine, benzyldimethylamine,allyldimethylamine, methallyldiethylamine, triethylamine,benzyldiethylamine, methylmorpholine, pyridine, picoline, or the like.

The halomethylation step is performed with formaldehyde or with arevertible polymer thereof, such as alpha-trioxymethylene, or othercompound readily yielding formaldehyde, such as dichloromethyl ether ora formal, such as dimethyl formal or diethyl formal, and a hydrogenhalide in excess. The temperature of the halomethylation reaction may befrom 0 to C. If desired, the reaction may be effected in the presence ofan acidic catalyst, such as zinc chloride, chlorosulfonic acid, orsulfuric acid. The ethers of 3,5-dimethylphenol and aliphatic alcoholsof one to four carbon atoms are best halomethylated at lowertemperatures, such as 0 to 25 C. without a catalyst, particularly whenonly one halomethyl group is to be introduced or even two halomethylgroups are to be introduced. More vigorous reaction conditions, such asthe presence of one of the indicated catalysts or elevated temperatures,are necessary for the introduction of another halomethyl group. This isparticularly true in regard to halomethylation of ethers withlongchained substituents. Halomethylation is desirably carried out in aninert solvent such as a hydrocarbon or a chlorinated solvent.

In one method for the conversion of a halomethylated phenyl ether to thequaternary ammonium compound, a halomethylated phenyl ether and atertiary amine may be reacted directly, although it is generally moredesirable to effect the reaction in an organic solvent, such as benzene,toluene, xylene, ethylene dichloride, nitromethane, ethyl acetate,naphtha, or the like. The reaction mixture is heated to 20 to C.,usually under reflux if a solvent is used, until the quaternization issubstantially completed.

The same general procedure is followed when the halomethylated phenylether is first reacted with a secondary amine and the tertiary aminethus formed reacted with an alkylating agent. This method permits asomewhat greater choice of N-substituents, but is not applicable, ofcourse, where such groups as pyridine may be desired.

The reaction product is usually separated from the reaction mixture byevaporation of solvent or crystallization. Purification by such steps ascharcoaling, solvent-extracting, or the like may be used.

Preparation of typical quaternary ammonium compounds of this inventionis illustrated in the following examples.

Example 1 A mixture of 47 parts of paraformaldehyde, 108 parts of3,5-dimethylanisole, 57.5 parts of concentrated hydrochloric acid with360 parts of carbon tetrachloride as solvent was agitated and a rapidstream of dry hydrogen chloride passed in over a period of five hourswithout heating, and for an additional two hours at 70 C. The solidwhich formed was washed by decantation and dried in vacuo. There wasthus recovered 168.5 parts of a crystalline solid, which melted at122-126 C. After recrystallization from a mixture of benzene andligroin, the chloromethylation product melted at l35-l37 C. By analysis(Cl, 29.4; theory 30.4) it corresponded tobischloromethyl-3,5-dimethylanisole.

Ten parts of the chloromethylation product and 13.4 parts ofbenzyldimethylamine dissolved in 20 parts of benzene were heated for tenhours at 50 C. The product was removed by filtration and dried. Therewas thus obtained 21.7 parts of the colorless, crystalline diquaternarysalt. The analysis of this salt,

Cl, 14.5; theory 14.1 N, 5.39; theory 5.56,

indicated practically complete conversion to the desired quaternaryform, the benzyldimethylamine diquaternary salt of bis-chloromethyl-3,5-dimethylanisole.

Example 2 C1, 18.6; theory 19.3 N, 3.68; theory 3.80)

showed this compound to be the benzyldimethyiamine monoquaternary saltof bis-chloromethyl 3,5-dimethylanisole, which behaves as a strong acid.

Example 3 A mixture of 48 parts of paraformaldehyde and 54.4 parts of3,5-dimethylanisole in 160 parts of carbon tetrachloride was agitated atC. and 15.1 parts of cholorosulfonic acid added over a period of two andone-half hours, the temperature being held at 80 C. or less by cooling.After one hour of additional stirring, the mixture was poured onice-water and filtered. The crude product was recrystallized from amixture of henzene and ligroin to yield 63 parts of thehischloromethylation product melting at 125-127 C. The same product canbe obtained in a similar manner from the chloromethylation product .of3,5-dimethylaniso1e previously described.

When recrystallized once again, the material melted at 129130 C.Analysis showed:

Cl, 36.3; theory 37.8 C, 51.5; theory 51.4 H, 5.63; theory 5.35.

A mixture of 15 parts of the chloromethylation product, 23 parts ofbenzyldimethylamine and 86 parts of benzene was refluxed seven hours. Itwas filtered to yield, after dryin 28 parts of a yellow solid materialessentially water-soluble, corresponding in composition to thebenzyldimethylamine quaternary salt of trischloromethyl-3,5-dimethylanisole.

1 Example 4 Seventy-five parts of the chloromethylation productdescribed in Example 1 was dissolved in 500 parts of benzene; thesolution was cooled in ice-water and trimethylamine gas passed in at afairly rapid rate until no more heat was evolved. Precipitation of theproduct was complete in one hour. The white, crystalline product wasfiltered ofi and dried in vacuo to yield 120 parts of the quaternarysalt. By analysis this proved to be 6 the trimethylamlne diquatemarysalt of his chloromethyl-3,5-dimethy1anisole.

Example 5 To a solution of 56 parts of potassium hydroxide in 355 partsof ethanol was added 122 parts of 3,5-dimethylphenol. The solution wasbrought to reflux and 272 parts of n-amyl chloride added dropwise. Themixture was refluxed 14 hours with agitation, the precipitated saltfiltered oil, and the alcohol removed from the filtrate by distillation.The residue was distilled in vacuo, yielding 115.5 parts of product,boiling at to C. at 25 mm. Hg. The distillate was washed twice with 150parts of 10% potassium hydroxide, then with water, and redistilled.There was obtained 76 parts of 3,5-dimethylphenyl amyl ether, boiling at145 to 148 C. at 25 mm. Hg, having the analysis C, 81.6; theory 81.3 H,10.5; theory 10.4.

A mixture of 22 parts of paraformaldehyde, 70 parts of the above ether,118 parts of concentrated hydrochloric acid, and 400 parts of carbontetrachloride as solvent was agitated and dry hydrogen chloride passedin while the mixture was cooled during the course of one and one-halfhours. The reaction mixture was then heated at 70 C. for four hours. Theorganic layer was separated, washed with water, and concentrated invacuo. The resulting product was dissolved in benezene, rewashed withwater, and again concentrated by heating in vacuo to remove solvents.There was thus obtained 70 parts of the monochloromethylation product, aviscous, light yellow liquid, giving the analysis 01, 13.8; theory 14.8C, 70.8; theory 70.8 H, 8.69; theory 8.40.

Example 6 3,5-dimethylphenyl dodecylether was prepared in similar mannerto the amyl ether from 28 parts of potassium hydroxide, 167 parts ofdodecyl bromide, and 61 parts of 3,5-dimethylpheno1 in parts ofisopropanol as solvent. After one distillation there was obtained 113parts of the ether, boiling at to 200 C. at 1 mm., having the analysis:

C, 80.2; theory 82.8 H, 10.9; theory 11.7.

A mixture of 233 parts of 3,5-dimethylphenyl dodecyl ether, 37.5 partsof paraformaldehyde, and 350 parts of concentrated hydrochloric acid wasagitated and dry hydrogen chloride passed in for two hours withoutexternal heat being applied and for ten hours at steam-bath temperature.The product layer was dissolved in benzene, washed with water, driedover anhydrous sodium sulfate, and the benzene removed in vacuo on thesteam-bath. There was obtained aaeaaia Cl, 9.29; theory 10.4.

The quaternary salt was prepared from 180 parts of the chloromethylationproduct and 75 parts of benzyldimethylamine in 175 parts of benzene assolvent at reflux for six hours. The

solvent was removed by heating on the steambath at 30-35 mm. to yield230 parts of the quaternary salt as a yellow, waxy solid. The saltcorresponded in composition to the benzyldimethylamine quaternary saltof chloromethyl- 3,5-dimethylphenyl dodecyl ether.

Example 7 In the same manner as the dodecyl ether above, from 122 partsof 3,5-dimethylphenol, 305 parts of cetyl bromide, 56 parts of potassiumhydroxide and 275 parts of isopropanol was obtained 250 parts of3,5-dimethylphenyl cetyl ether, boiling between 187 and 220 C. at 1.5mm. of Hg, having the analysis C, 81.6; theory 83.3 H, 11.9; theory12.1.

Hydrogen chloride gas was passed rapidly into a mixture of 200 parts ofthe ether, 24 parts of paraformaldehyde, and 350 parts of concentratedhydrochloric acid during the course of 18 hours, the reaction andisolation being as described above for the dodecyl homologue. There wasobtained 208 parts of a brown liquid, having the analysis Cl, 8.25;theory 9.00.

Cl, 5.94; theory 6.70 N, 2.80; theory 2.65

and this corresponded to the benzyldimethylamine quaternary salt ofchloromethyl-3,5-dimethylphenyl cetyl ether.

Example 8 Preparation throughout was similar to that for the dodecyl andcetyl ethers described above. From 98 parts of 3,5-dimethylphenol, 333parts of octadecyl bromide, and 45 parts of potassium hydroxide in 320parts of methanol was obtained 207 parts of 3,5-dimethylphcnyl octadecylether, boiling at 205 to 235 C. at 1.5 to 2 mm, a colorless, waxy solidon cooling.

Hydrogen chloride gas was passed rapidly into a mixture of 207 parts of3,5-dimethylphenyl octadecyl ether, 25 parts of paraformaldehyde and 350parts of concentrated hydrochloric acid at steam-bath temperature for 19hours. The product was isolated as described for the dodecyl ether.There was thus obtained 210 parts of the clear orange liquidmonochloromethylation product, which, on standing, solidified to a waxysolid.

The quaternary salt was prepared from 100 parts of thechloromethylationproduct and parts of benzyldimethylamine in 130 partsof benzene at steam-bath temperature for six hours. The benzene wasremoved by heating in vacuo on the steam-bath, and the product freed ofamine over sulfuric acid in vacuo.

There was thus obtained parts of the brown, waxy quaternary saltcorrespondingto the benzyldivmethylamine quaternary salt of chloromethyl3,5-dimethyiphenyl octadecyl ether.

Example 9 To a solution of 20 parts of bis-chloromethyl-3,5-dimethyianisole in 110 parts of benzene was added 13.6 parts ofpyridine dropwise at room temperature while the mixture was agitated.After the mixture has stood at room temperature for two hours, it wasstirred three hours at reflux, and the product was then removed anddried in vacuo at steam-bath temperature. Twenty parts of thehygroscopic, colorless, crystalline quaternary was obtained,corresponding in composition to pyridine diquaternary salt ofbis-chloromethyl-3,5-dimethylanisole.

Example 10 A solution of 71 parts of 3,5-dimethylanisole in 400 parts ofsym.-tetrachloroethane was cooled to 0 C. and 71 parts of anhydrouspowdered aluminum chloride added while the solution was stirred. To thismixture there was slowly added 40.8 parts of acetyl chloride while thereaction mixture was stirred and cooled so as to keep the temperaturebelow 10 C. The mixture was stirred with cooling for three hours, thenwas allowed to come to room temperature and was left standing overnight.It was then poured on chopped ice and the tetrachloroethane layerfiltered, dried, and distilled through a Vigreux column. The fractionboiling at 147-150 C. at 24 mm. was collected. This amounted to 74.8parts of acetyl-3,5-dimethy1anisole, a clear liquid crystallizing oncooling. The material thus obtained was analyzed as follows:

C, 73.0% (theory 74.1) H, 7.82% (theory 7.86).

A mixture of 31 parts of the above acetylated ether, 10.5 parts ofparaformaldehyde, and 88 parts of concentrated hydrochloric acid washeated and stirred on the steam-bath while hydrogen chloride gas waspassed in rapidity. When the product formed a gum, parts ofsym.-tetrachloroethane was added as solvent, and hydrogen chloride gaspassed in for another three hours. The tetrachloroethane layer wasseparated and dried in vacuo giving a semi-crystalline product which wasrecrystallized twice from a mixture of benzene and ligroin to yield 13.5parts of a somewhat sticky, crystalline solid, melting from 123 to 127C., corresponding in composition tobis(chloromethyl)acetyl-3,5-dimethylanisole.

A mixture of 13.5 parts of this chloromethylation product and 14 partsof benzyldimethylamine was heated in 25 parts of benzene at 60-70 C. forten hours. The benzene was removed. By

titration, quaternization of both chloromethyl groups was incomplete,and the crude quaternary was again refluxed in benzene with fiveadditional parts of benzyldimethylamine for eight hours. The product wasfiltered and dried in vacuo to yield 23 parts of the colorless,crystalline diquaternary salt, benzyldimethylamine diquaternary salt ofbis-chloromethyl-acetyl-3,5- dimethylanisole. The equivalent weight ofthis compound by ionizable chlorine was found to be 279 (theory 273).

Example 11 A mixture of 49 parts of acetyl-3,5-dimethylanisole, 125parts of amalgamated zinc, 135 parts of xylene, and 30 parts ofconcentrated hydrochloric acid was stirred and heated at reflux foreight hours with continuous passage of dry hydrogen chloride. The xylenelayer was then separated, the xylene removed, and the product distilledat 85 C. at 25 mm. to 112 C. at 30 mm. to yield 24 parts of thecolorless liquid product, ethyl-3,5-dimethylanisole.

A mixture of 24 parts of this ether with 9 parts of paraformaldehyde, 60parts of concentrated hydrochloric acid, and 60 parts of glacial aceticacid was heated on the steam-bath with stirring while a rapid stream ofdry hydrogen chloride was passed in for three hours. There was added 60parts additional of glacial acetic acid and the reaction was continuedan additional four hours. The product was dissolved in ethylenedichloride and washed with water. The ethylene dichloride was removed byheating in vacuo. The product was again treated with 70 parts ofethylene dichloride, 30 parts of glacial acetic acid, 60 parts ofconcentrated hydrochloric acid, and 5 parts of paraformaldehyde for fivehours more and isolated in the same way to yield 21 parts of thechloromethylated product as a sticky solid.

A mixture of 21 parts of the chloromethylated product and 25 parts ofbenzyldimethylamine was refluxed in 88 parts of benzene for eight hours.The solid was filtered ofi, washed, and dried to yield 35.5 parts of thequaternary salt, the henzyldimethylamine quaternary salt ofchloromethylated ethyl-3,5-dimethylanisole.

The equivalent weight by ionizable chlorine is 325 as compared to thetheory for monoquaternary salt. 348; for diquaternary salt, 266. Theproduct is, therefore, a mixture of the two.

Example 12 (a) A mixture of 17.4 parts of bis(chloromethyl)-3,5-dimethy1anisole and 17 parts of N-methylpiperidine was refluxed in80 parts of benzene for five hours. A resinous solid separated from thesolution. It was removed, washed with benzene, and dried to yield 26.2parts of the yellowish solid quaternary salt, the N-methylpiperi- Theequivalent weight by ionizable chlorine is 191 (theory 217).

Example 13 A mixture of 24 parts methallyldimethylamine and 20.5 partsof bis(chloromethyl) -3,5-dimethylanisole in 90 parts of benzene wasrefluxed for five hours. The reaction mixture was again refluxed with 10parts of additional amine in 65 parts of benzene for five hours. Therewas thus obtained 21.7 parts of the colorless, crystalline diquaternarysalt, methallyldimethylamine diquaternary salt ofbis-chloromethyl-3,5-dimethylanisole.

The equivalent weight by ionizable chlorine was 210 (theory 216).

Example 14 Fifty parts of bis(chloromethyl) -3,5-dimethylanisole, 153parts of a 25% solution of-dimethylamine in water, and 19.8 parts ofsodium hydroxide were placed in an autoclave and heated at 150 C. withrocking for five hours. The contents were then ether-extracted and driedover anhydrous sodium sulfate. The ether was removed and the productdistilled. Bis(dimethy1- aminomethyl)-3,5-dimethylanisole was collectedat l-l82" C. at 20-22 mm. Forty-two parts of this product was obtainedas a clear, thick oil. The neutralization equivalent of this materialwas (theory 125).

A mixture of 12 parts of bls(dimethylaminomethyl) -3,5-dimethylanisoleand 18 parts of benzyl bromide was refluxed in parts of benzene foreight hours. Quaternization was found to be incomplete at this point.The reaction product was, therefore, refluxed with an additional eightparts of benzyl bromide in 100 parts of benzene for an additional fivehours. The solid 50 formed was removed, well washed by grinding underpetroleum ether, and dried in vacuo to yield 14.6 parts of the benzylbromide diquaternary salt ofbis(dimethylaminomethyl)-3,5-dimethylanisole.

In similar manner, the diquaternary salt was prepared using benzylchloride to yield the same compound as previously obtained byquaternization of bis(chloromethyl)-3,5-dimethylanisole withbenzyldimethylamine.

Example 15 A solution of 97.3 parts of 3,5-dimethylanisole in 560 partsof tetrachloroethane was cooled to 10 C. in an ice-bath and 98.4 partsof anhydrous aluminum chloride added rapidly while the solution wasstirred. To this mixture was added 225 parts of stearoyl chloride whilethe reaction mixture was cooled and stirred at such a rate that thetemperature did not rise above 10 C. Stirring and cooling were continuedfor five hours, and the mixture was then allowed to stand at roomtemperature overnight. It was then poured on ice and thetetrachloroethane removed by steamdistillation. On cooling, the productsolidified as a waxy, tan-co ored solid. This was filtered, melted, andstirred with hot 10% sodium car bonate solution, cooled, and refiltered.It was then dried in vacuo on the steam-bath to yield 332 parts of crudeproduct. This product was dissolved in hot ligroin, filtered and cooledto yield 132 parts of the pure product, stearoyl-3,5-dimethylphenylmethyl ether, a soft, white powder melting at 55-57 C., giving analysesas follows:

Per cent C, 80.5 (theory 80.6) and Per cent H, 11.7 (theory 11.4).

rine content of 7.36% (theory for the monochloromethylation product is7.88%).

A mixture of 20 parts of the chloromethylation product with 6 parts oibenzyldimethylamine in 70 parts of benzene was heated under reflux whilethe mixture was stirred at 50-60 C. for 24 hours. The benzene was thenremoved in vacuo to yield 22 parts of the benzyldimethylamine quaternarysalt of chloromethyl-stearoyl-3,5-dimethylanisole, a whitish powder,giving the following analyses:

per centCl, 5.48 (theory 6.06) and per cent N, 2.39 (theory 2.39).

Example 16 Two hundred fifty parts of mossy zinc were amalgamated bystirring with 25 parts ofmercuric chloride, 14 parts of concentratedhydrochloric acid, and 300 parts of water for ten minutes. The aqueouslayer was poured off. concentrated hydrochloric acid added to half-coverthe zinc, and a solution of 100 parts of stearoyl- 3,5-dimethylanisolein 260 parts of xylene added. The mixture was stirred and refluxed whilehydrogen chloride gas was passed through for 21 hours. The xylene layerwas separated, washed with water, and the xylene removed by distillationin vacuo. This left a residue which solidified when cool. It wasrecrystallized from ligroin. There was thus obtained 65 parts of white.waxy solid, octadecyl 3,5-dimethylanisole, melting at 54.5-56.5 C. whichgave the following analyses:

per cent C, 81.0 (theory 83.5) and per cent H, 12.3 (theory 12.4).

A mixture of 63 parts of the above ether, 5.3 parts of paraformaldehyde,60 parts of concentrated hydrochloric acid and 75 parts of glacialacetic acid was heated and stirred under reflux while HCl gas was passedin for 16 hours. The resulting product was dissolved in benzene andwashed with water. The benzene was then removed. After recrystallizationfrom ligroin, 52 parts of white powder. melting at '75-77 6.,chloromethyl octadecyl 3,5-dimethyianisole, was obtained. having achlorine analysis of 7.78% (theory 8.16). v

A mixture of 46 parts of the chloromethylated ether and 16 parts ofbenzyldimethylamine in 88 parts of benzene was refluxed for eight hourswhile the mixture was stirred, the benzene was removed in vacuo, and thesoft solid resulting was dried in vacuo over sulfuric acid to removeexcess amine. There was obtained as a yellowish,

waxy solid 54 parts of the benzyldimethylamine quaternary salt ofchloromethyl octadecyl-3,5- dimethylanisole.

Example 17 Carbon 79.0% (theory 80.0%) Hydrogen 7.74% (theory 8.15%).

Hydrogen chloride gas was passed into a mixture of 35 parts ofbis-3,5-dimethylphenoxyethane, 25 parts of 37% formaldehyde solution, 70

parts of concentrated hydrochloric acid, and 160 parts of carbontetrachloride. The mixture was heated with reflux and agitation forseven and one-half hours. The carbon tetrachloride layer was evaporatedto dryness to yield a product which was ground under water in a mortarand dried in vacuo to yield 38 parts of the amorphousbis-chloromethylation product. From the chlorine analysis of thismaterial (20.8%) there were 2.2 chloromethyl groups per molecule.

A mixture of 30 parts of this chloromethylation product and 23.8 partsof benzyldimethylamine was heated for three and one half hours at C. in100 parts of dioxane. The solvent was poured off, the hard, amorphoussolid product broken out of the flask, triturated with anhydrous ether,filtered and dried to yield 45 parts of the quaternary salt, thebenzyldimethylamine quaternary salt ofbis-chloromethyl-sym.-bis-3,5-dimethylphenoxyethane.

Example 18 To a solution of 360 parts of sodium 3,5-dimethylphenolate in400 parts of ethanol were added 2 grams of 250-mesh copper powder and,drop- -wise at reflux, 202 parts of trimethylene dibro- Carbon 80.6%(theory 80.5%) Hydrogen 8.34% (theory 8.45%).

Hydrogen chloride gas was passed into a mixture of '71 parts of1,3-bis(3,5-dimethylphenoxy) propane, 15 parts of paraformaldehyde,parts of concentrated hydrochloric acid, and 160 parts of carbontetrachloride for three hours. The crude product was removed byfiltration through fritted glass as a soft, gummy material whichhardened on drying to an amorphous solid. There was thus obtained 62parts of the desired product. From the chlorine analysis, 17.0%, thisproduct contained 1.8 chloromethyl groups per molecule.

A mixture of 30 parts of this chloromethylation product and 19.5 partsof benzyldimethylamine in parts of benzene was heated for four hours at45-60 C. The product crystallized and was removed by filtration anddried in vacuo to yield 49.5 parts of the benzyldimethylamine quaternarysalt of bis-chloromethyl-1,3-bis 3,5 dimethylphenoxypropane. Theequivalent weight by ionizable chlorine was 356 (theory 340).

Example 19 Anhydrous hydrogen bromide was passed into a mixture of partsof 3,5-dimethylphenyl octadecyl ether, 16 parts of paraformaldehyde,parts of ethylene dichloride, 75 parts of water, and 10 parts of glacialacetic acid at room temperature for eight hours, then at 40-50 C. fortwelve hours. The product separated as a light tan solid which waswashed in sodium bicarbonate solution and dried to yield 140.4 parts ofthe bro-momethylation product. This appeared to be 13 mainly thedibromomethylation product, the analyses of which follow:

Bromine, 25.01%; theory: 17.2% (mono), 28.6%

Carbon, 62.95%; theory:

Hydrogen, 9.01%; theory: 10.2% (mono), 8.58%

A solution of 15 parts of the above bromomethylation products, parts ofbenzyldimethylamine, 8.2 parts of benzene, and 20 parts of nitromethanewas heated at 40-50 C. for hours with stirring. The solvents werefiltered off and the brown, waxy material that remained dried in vacuowith gentle heating. There resulted 11.7 parts of a brown solidquaternary salt, the benzyldimethylamlne quaternary salt ofbromomethylated 3 5-dimethylphenyl octadecyl ether, which was readilywater-soluble.

The molecular weight by ionizable chlorine was 510 (theory: 415 (di) 602(mono).

The compounds of this invention can be dissolved in water and theresulting solution applied to cellulosic materials by dipping, padding,or spreading. The excess solution may thus be re moved and the treatedcellulosic material dried and heated to temperatures from 220 to 320 F.Times of heating may vary from an hour to two or three minutes. Thecompound reacts with the cellulose. thus where Z represents a cellulosegroup carrying a hydroxyl group. After the reaction, the cellulosic69.5% (mono), 59.9%

ZOCH

CE CH9 material has new properties which are retained after washing.Nitrogenous decomposition products can be removed, but there is a.definite increase in weight of the treated cellulosic material.

Compounds having two or more quaternary am- I monium groups not onlychange the handle of cellulosic fabrics but also stabilize them againstchanges in dimensions. Compounds, whether monoor poly-substituted, alterthe handle, water-absorbency, and dyeing properties of fabrics, yarns,or fibers treated therewith.

In a series of applications diflerent solutions at a uniformconcentration of 10% were applied to pieces of a viscose rayon twill.Each piece of fabric was then dried and heated at 300 F. for 30 minutes.It was then washed in a hot water solution of a buffer salt at pH '7,rinsed in water several times, and then washed in hot alcohol. Fromweights taken at suitable times the amount of the compound reacting withthe fabric was determined. The actual change in weight is convenientlycompared with the theoretical gain in weight which should have resultedon the basis of the theoretical reaction shown above. See the table.

In the summary below the compounds shown are identified by the number ofquaternary ammonium methyl groups and by indication of startingmaterials. For each compound there is given the percentage of thetheoretical increase in i. 14 weight which occurs. In the table allquaternary compounds were prepared with the same tertiary amine,benzyldimethylamine, in order to hold constant this ariable. In everycase the ether is substituted on the 3- and 5-positions of the phenylring with methyl groups.

Table Weight Gain N f in Per Cent 0! 263;: Parent Ether Theory 1 phenylmethyl 40 2.-.- do 01 88 i chlornmothylnhenyl methyL. 54 3,.phenylmethyL; 72 i phonyl amyl. 79 63 1 phenyl dodecyl 39 2 phenylethyl. 122 (104) 2 bis (phenoxyi propane-l,3 78 93 2.-bis(phenoxy)ethane llfl (134) 3 sym .-phenoxyethyl. (1%) 118 1. phenylcetyl 43 (47) 1 pheuyl octadecyl 2. aeetylphenyl methyl 84 (85) lethylphenyl methyl (Q2) 2.. phenyl methyl Bromine 75 72 phenyl methylChlorine 61 78 a-Results with 4% ammonium chloride as catalyst.

b-Results with 4% sodium hydroxide added.

( )Results without added catalyst.

'Made by reaction with sec. amino and roaction with indicated benzylhalide.

Similar results were obtained with other compounds. For example, theN=methylpiperidino derivative of bis-(chloromethyl)-3,5-dimethylanisolewith sodium hydroxide as catalyst gave a weight gain of 50%. ThecomparableN-methylmorpholino derivative gave weight gains approximatingin a. number of tests. The comparable methallyldimethyl dlquaternary compound gave a weight gain of 51%. These tests show that the compounds ofthis invention react with cellulose by a permanent chemical linkage,resulting in modification of the cellulose. In place of the specificcompounds named above, there may be used any other of the compoundscoming within the general formula given above. Within this generalformula there are some subgroups of special interest. One subgroup maybe represented by the formula CH CH:

where R0 is a monovalent hydrocarbon group, particularly an aliphatichydrocarbon group of one to eighteen carbon atoms, R, is an alkyl groupor an acyl group, particularly groups of one to eighteen carbon atoms, mis an integer from one to three, 11 represents a number having valv ofzero and one, Z is the group as has been previously defined. Thissubgroup or compounds is claimed in the instant case.

Another subclass of particular interest be represented may CHI-I (R H 2as previously defined. The subgroup of compounds in which R0 is adivalent group is claimed in application Serial No. 769,529, filed oneven date by de Benneville and Bock.

We claim:

1. Compounds of the formula wherein R0 is a monovalent aliphatichydrocarbon group of one to eighteen carbon atoms, R is a group havingnot over eighteen carbon atoms from the class consisting of alkyl groupsand acyl groups from monocarboxylic acids consisting of an aliphatichydrocarbon radical and a carboxyl group, m is an integer from one tothree, a is a number from zero to one, the sum of m and a being not overthree, R. taken individually represents a member of the class consistingof methyl, ethyl, allyl, methallyl, and benzyl groups; R" and R' takenindividually represent a member of the class consisting of methyl andethyl groups, R" and R' taken together represent a divalent saturatedaliphatic group from the class consisting of the ether chain andalkylene chains of four to five carbon atoms which jointly with thenitrogen form a heterocycle, R, R", and R taken together represent 16 ahydrocarbon chain which jointly with the nitrogen forms a pyridine ring,and X is an anion.

2. Compounds of the formula wherein R0 is an alkyl group of not overeighteen carbon atoms.

3. Compounds of the formula CLHu CHzCaHu 0 HIN/ on cm P wherein X is ahalogen.

4. Compounds of the formula wherein X is a halogen.

5. The compound of the formula PETER L. DE BENNEVILLE. LEONARD J.ARMSTRONG. LOUIS H. BOCK.

on on REFERENCES CITED UNITED STATES PATENTS '0 U Number Name Date2,033,092 Bruson Mar. 3, 1936 2,036,916 Bruson Apr. 7, 1936 2,260,967Bruson Oct. 28, 1941 2,383,775 Craig et a1. Aug. 28, 1945 2,395,336McMullen et al. Feb. 19, 1946 OTHER REFERENCES Auwers: Llebigs Annalen,vol. 334 (1904), pp. 271, 303 to 307.

Braun et al.: Liebigs Annalen, vol. 490 (1931) pp. 198 and 199.

1. COMPOUNDS OF THE FORMULA
 5. THE COMPOUND OF THE FORMULA 